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United States Patent | 5,792,830 |
Noding ,   et al. | August 11, 1998 |
Described is a process for preparing polyaniline polymer which includes contacting aniline monomers with (a) hydrogen peroxide, (b) at least one acid, including hydrogen chloride, hydrogen bromide, or a mixture thereof, and (c) a catalytic amount of at least one metal-containing compound or complex, under reaction conditions sufficient to form a polymerization reaction product containing a polyaniline polymer. It has been discovered that the processes described herein provide means to prepare polyaniline having a relatively high conductivity at a high degree of aniline monomer conversion using hydrogen peroxide as an oxidant.
Inventors: | Noding; Stephen A. (Brusly, LA); Babinec; Susan J. (Midland, MI); Scortichini; Carey L. (Midland, MI) |
Assignee: | The Dow Chemical Company (Midland, MI) |
Appl. No.: | 762481 |
Filed: | December 9, 1996 |
Current U.S. Class: | 528/422; 252/500; 525/540; 528/210; 528/212; 528/214; 528/391 |
Intern'l Class: | C08L 049/00; C08F 006/00 |
Field of Search: | 528/422,210,212,214,391 525/540 252/500 |
5324453 | Jun., 1994 | Cao et al. | 528/422. |
5371182 | Dec., 1994 | Galaj et al. | 528/422. |
5403913 | Apr., 1995 | MacDiarmid et al. | 528/422. |
5420237 | May., 1995 | Zemel et al. | 528/422. |
5436317 | Jul., 1995 | Jarvinen et al. | 528/422. |
5470505 | Nov., 1995 | Smith et al. | 252/500. |
5574131 | Nov., 1996 | Ona | 528/422. |
Foreign Patent Documents | |||
062 00017 | Oct., 1994 | JP. | |
94/10327 | May., 1995 | WO. |
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TABLE 1 __________________________________________________________________________ ›acid!, Temp. ›aniline!, Time yield, Example Acid molar (.degree.C.) molar (hr.) R (%) .sigma., S/cm __________________________________________________________________________ 1 HCl 1.6 26-29 0.32 3.5 1.25 78 0.63 2 HCl 1.6 25.5-27 0.32 2.7 1.00 61 0.95 3 HCl 1.6 26-29.5 0.32 4.0 1.50 78 0.31 4 HCl 1.6 27-30 0.79 3.0 1.25 80 0.32 5 HCl 1.6 8-9 0.78 19.0 1.25 66 0.65 6 HCl 3.9 6-8.5 0.77 21.5 1.25 85 2.40 7 HCl 3.9 6-7 0.77 20.0 1.15 77 3.64 8 HCl 6.0 0-1 0.78 22.0 1.25 49.6 0.059 9 HBr 1.6 25-28 0.81 3.0 1.25 85.3 1.08 10 10 mole 1.6 24-27 0.79 3.7 1.25 79.5 4.37 % HBr/ 90 mole % HCl 11 25 mole 1.6 24-29 0.79 3.5 1.25 79.4 3.59 % HBr/ 75 mole % HCl __________________________________________________________________________
TABLE 2 ______________________________________ Polymerize Oxidize Acid Catalyst aniline m-nitroaniline ______________________________________ HCl Fe (II) + - HCl Fe (III) + - HCl Cu (I) + - HCl Cu (II) + - HCl Nb (V) - - HCl Ru (III) + - HBr Fe (II) + - HBr Cu (I) + - HBr Cu (II) + - H.sub.2 SO.sub.4 Fe (II) + + H.sub.2 SO.sub.4 Fe (III) + + H.sub.2 SO.sub.4 Cu (II) - - HClO.sub.4 Fe (II) + + HClO.sub.4 Fe (III) + + HClO.sub.4 Cu (II) - - HNO.sub.3 Fe (II) + + HNO.sub.3 Fe (III) + + H.sub.3 PO.sub.4 Fe (II) - - H.sub.3 PO.sub.4 Fe (III) - - H.sub.3 PO.sub.4 Cu (II) - - HCl Mo (VI) - - HCl Co (II) - - HCl Mn (II) - - HCl Ni (II) - - H.sub.2 SO.sub.4 Co (II) - - H.sub.2 SO.sub.4 Mn (II) - - H.sub.2 SO.sub.4 Ni (II) - - HCl Sb (III) - - HCl + Fe (II) + - pTSA H.sub.2 SO.sub.4 + Fe (II) + - NH.sub.4 Cl + BSA HBr + Fe (II) + - pTSA ______________________________________
TABLE 3 ______________________________________ (Reaction Mixture Compositions and Conditions for Examples 12-19) Composition Temp. Time Example (molar) (.degree.C.) (hrs) ______________________________________ 12 aniline (0.4); NH.sub.4 Cl (1.6); H.sub.2 SO.sub.4 25-29; 22.5 BSA (0.4) 13 aniline (0.4); HCl (1.2); pTSA (0.4) 25-28 5.8 14 aniline (1.6); HCl (2.0) 26-29 6.5 15 aniline (0.4); HBr (0.6); pTSA (0.4) 25-27 6.3 16 aniline (0.84); HCl (1.6) 25-28 3.5 17 aniline (0.3); HCl (3.2); pTSA (0.3) 5-7 16.4 18 aniline (0.77); HCl (1.6) 25-27 22.4 19 aniline (0.81); HCl (1.6) 25-27 23.4 ______________________________________
TABLE 4 ______________________________________ (Results for Examples 12-19) % Example % yield conversion % selectivity % efficiency .sigma. (S/cm) ______________________________________ 12 74 86 86 56 0.78 13 74 86 86 55 4.2 14 63 74 86 63 0.1 15 65 84 78 50 0.32 16 81 83 97 81 1.9 17 69 90 76 54 0.16 18 76 81 94 76 0.17 19 71 74 96 71 0.72 ______________________________________